US6315925B1 - Nonylated diphenylamines - Google Patents

Nonylated diphenylamines Download PDF

Info

Publication number
US6315925B1
US6315925B1 US09/503,264 US50326400A US6315925B1 US 6315925 B1 US6315925 B1 US 6315925B1 US 50326400 A US50326400 A US 50326400A US 6315925 B1 US6315925 B1 US 6315925B1
Authority
US
United States
Prior art keywords
area
mixture
diphenylamine
tert
butyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US09/503,264
Other languages
English (en)
Inventor
Beat Michael Aebli
Samuel Evans
Sandor Gati
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
Ciba Specialty Chemicals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Specialty Chemicals Corp filed Critical Ciba Specialty Chemicals Corp
Priority to US09/503,264 priority Critical patent/US6315925B1/en
Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AEBLI, BEAT MICHAEL, EVANS, SAMUEL, GATI, SANDOR
Application granted granted Critical
Publication of US6315925B1 publication Critical patent/US6315925B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines

Definitions

  • the invention relates to a mixture of nonylated diphenylamines, to a process for the preparation of that mixture and to the use thereof as an additive for stabilising organic products that are subjected to oxidative, thermal and/or light-induced degradation.
  • Additives are added to numerous organic products widely used in engineering, for example to lubricants, hydraulic fluids, metal-working fluids, fuels or polymers, to improve their performance properties.
  • additives that effectively inhibit the oxidative, thermal and/or light-induced degradation of those products and thereby considerably increase their useful life.
  • U.S. Pat. No. 2,943,112 describes anti-oxidants from the group of the alkylated diphenylamines that are prepared by reaction of diphenylamine with alkenes in the presence of mineral acids and large quantities of acid clays as catalysts. Alkylation of the diphenylamine with alkenes, for example nonene, results in mixtures of mono- and di-alkylated diphenylamine. In that process, relatively large quantities of the starting material, generally from 6 to 12% diphenylamine, are not reacted, which reduces the anti-oxidative efficacy of the alkylated diphenylamines, leads to the deposition of sludge and imparts undesirable toxic properties to the product. Reaction with additional alkenes is proposed as an alternative to the distillative separation of the starting material from the products.
  • U.S. Pat. No. 3,496,230 describes the preparation of a mixture of 80% dinonyidiphenylamine and 15% nonyldiphenylamine in the presence of Friedel-Crafts catalysts of the aluminium chloride type, but that mixture still has a diphenylamine content of 2% (see therein the information in Example 2).
  • the preparation of that mixture is especially disadvantageous since it is contaminated by traces of chlorine, metal compounds and undesirable by-products, e.g. N-alkylated diphenylamines and diphenylamines alkylated in the 2- and 2′-positions, is black in colour and is very viscous.
  • European Patent Application No. 387 979 describes the reaction of diphenylamine with an eight-fold excess of tripropylene. That process is also disadvantageous since, in addition to the large excess of tripropylene, it is also carried out in the presence of large quantities of acid-activated clays.
  • the problem underlying the present invention is to prepare a mixture of nonylated diphenylamines that comprises as large as possible amounts of dinonyidiphenylamine, especially 4,4′-dinonyldiphenylamine, in addition to nonyldiphenylamine, e.g. 4-monononyidiphenylamine, and as small as possible amounts of undesirable by-products, e.g. N-alkylated diphenylamines and diphenylamines alkylated in the 2- and 2′-positions.
  • That problem is solved by a inventive process which comprises alkylating diphenylamine with an excess of nonene or a mixture of isomeric nonenes in the presence of from 2.0 to 25.0% by weight, based on diphenylamine, of an acid earth and in the absence of a free protonic acid.
  • the invention relates to a mixture of nonylated diphenylamines that has a content in a gas chromatogram (GLC, on-column method) of:
  • nonyl groups in the main component dinonyldiphenylamine and in the co-component nonyidiphenylamine are in the 4,4′-position and the 4-position, respectively, of the diphenylamine.
  • mixtures wherein the nonyl groups are derived by reacting the diphenylamine with tripropylene.
  • the invention relates to a mixture comprising in a gas chromatogram:
  • the invention relates to a mixture comprising in a gas chromatogram:
  • At least 68.0% by area dinonyidiphenylamine means preferably from 68.0 to 78.0% by area, especially from 70.0 to 75.0% by area, dinonyldiphenylamine.
  • the statements “not more than 3.5% by area trinonyldiphenylamine” means from 1.0 to 3.5% by area, preferably from 1.5 to 3.5% by area, also preferably from 2.0 to 3.5% by area and especially from 2.5 to 3.5% by area.
  • the statement “not more than 3.0% by area trinonyldiphenylamine” means preferably from 1.0 to 3.0% by area, preferably from 1.5 to 3.0% by area, also preferably from 2.0 to 3.0% by area and especially from 2.5 to 3.0% by area, of that component.
  • not more than 1.0% by area diphenylamine means preferably from 0.1 to 1.0% by area, especially from 0.3 to 0.8% by area
  • not more than 0.8% by area diphenylamine means preferably from 0.3 to 0.8% by area, especially from 0.3 to 0.6% by area, of that component in a gas chromatogram.
  • the invention also relates to the product of the inventive process obtainable by alkylation of diphenylamine with an excess of nonene or a mixture of isomeric nonenes in the presence of from 2.0 to 25.0% by weight, based on diphenylamine, of an acid earth and in the absence of a protonic acid.
  • the invention also relates to the product of that inventive process, which has a kinematic viscosity of ⁇ 500 mm 2 /sec at 40° C.
  • the invention further relates to the process for the preparation of a mixture of nonylated diphenylamines comprising in a gas chromatogram
  • Suitable acid clays are, for example, active catalysts based on layered silicate, e.g. montmorillonites activated by mineral acids, such as sulfuric acid and/or hydrochloric acid, that preferably have a moisture content below 10%, especially below 5%, e.g. of the clays of the so-called Fuller type, e.g. types obtainable commercially under the names Fulcat®, e.g. types 20, 22 B and 40 (argillaceous earths activated by sulfuric acid), Fulmont® (Laporte Industries), e.g.
  • types XMP-4, XMP-3, 700 C and 237 or acid earths of types K5 and K10 (activated by hydrochloric acid), KS and KSF (activated by sulfuric acid) or KSF0 (activated by hydrochloric acid and sulfuric acid) produced by Südchemie, and earths based on bentonite, e.g. products of the type Filtrol® or Retrol® (Engelhard Corp.).
  • the products of the process are obtained when the alkylation is carried out, for example, at a temperature range from 120° to 250° C., especially at a temperature of from 150° to 220° C.
  • the process can be carried out by introducing the starting materials and the acid clays, as the catalyst, into a suitable reaction vessel and by heating to the temperatures specified.
  • the tripropylene may be added to the reaction at a later point in time.
  • the reaction is preferably carried out without the addition of organic solvents.
  • the reaction time may be several hours, especially from 5 to 20 hours, before a diphenylamine content of less than 1% is reached, which can be ascertained by the taking of samples and analytical determination.
  • the reaction is preferably carried out under elevated pressure, for example in an autoclave under a pressure of from 1 to 10 bar absolute pressure.
  • the acid clays used in the process can be removed from the reaction mixture by filtration, centrifugation or decanting, and are re-usable. In practice, they are used in an amount of from 5.0 to 20.0% by weight, especially from 5.0 to 10.0% by weight. If desired, the mixture is purified in customary manner, for example by distillation.
  • the process product has favourable viscosity characteristics.
  • Viscosity characteristics For example, in an Ubbelohde viscosimeter, low kinematic viscosities of ⁇ 500 mm 2 /sec at 40° C. are measured (ASTM D 445-94 method, micro-Ubbelohde 2.0-3.0 ml, Ubbelohde factor approx. 5). That value is lower than in the case of the products obtainable according to U.S. Pat. No. 3,496,230 by reaction with AlCl 3 which, with their intense coloration, are also less light-transmissive than the process products.
  • a mixture prepared according to Example 2 of U.S. Pat. No. 3,496,230 has the following composition and properties:
  • a mixture of 1% of that composition and 99% of a synthetic engine oil formulation based on a phosphorus content of 0.08% by weight is subjected to the test conditions of Test M 18, see Example 3 below. It has an induction period of 43 minutes compared with the induction period of 50 minutes that is obtained with the product according to Example 1.
  • a product prepared according to Example 4 of U.S. Pat. No. 3,496,230 has the following composition and properties:
  • a mixture of 1% of that composition, 1.8% of a diesel catalyst made from a mixture of 25% of an iron naphthenate solution, 5% of a copper naphthenate solution, both from Strem Chem USA, and the remainder STANCO 150 mineral oil from Esso, and 97.2% REOLUBE LPE 602 is subjected to the test conditions of test M 17. An induction period of 73 minutes is determined;
  • a mixture of 1% of that composition, 0.5% nitropentane and 98.5% REOLUBE LPE 602 from FMC exhibits according to the loading test M 17 an induction period of 69 minutes. If a mixture of 1% of that composition and 99% of a synthetic engine oil formulation based on a phosphorus content of 0.08% is subjected to the test conditions of Test M 18, an induction period of 44 minutes is obtained.
  • the product so prepared is analogously subjected to the test conditions of Test M 17. In that test, a considerably higher disadvantageous induction period of 56 minutes is measured.
  • the product having the high trinonyidiphenylamine content is also subjected to the conditions of Test M 18. An induction period of 44 minutes is determined.
  • the mixtures according to the present invention have an outstanding anti-oxidative action, which can be demonstrated by favourable HPDSC values (High Pressure Differential Scanning Calorimetry), e.g. 79 min. for Test M 17 (sample at 200° C./SX, 10 bar O 2 , 1% in REOLUBE LPE 602) or 50 min. for Test M 18 (sample at 200° C./SX, 8 bar NO x , 1% in M251/0.08% P (Shell)).
  • HPDSC values High Pressure Differential Scanning Calorimetry
  • Test M 17 sample at 200° C./SX, 10 bar O 2 , 1% in REOLUBE LPE 602
  • 50 min. for Test M 18 sample at 200° C./SX, 8 bar NO x , 1% in M251/0.08% P (Shell)
  • They can therefore be employed as additives in numerous organic products widely used in engineering, e.g. in lubricants, hydraulic fluids, metal-working fluids,
  • At least one stabilising mixture comprising dinonyldiphenylamine as the main component as defined hereinbefore and prepared according to the process of the invention.
  • a particular class of organic products subjected to undesirable oxidative degradation for which the mixtures according to the present invention are valuable stabilisers is formed by lubricants and operational fluids based on mineral oil or synthetic lubricants or operational fluids, e.g. carboxylic acid ester derivatives, that can be used at temperatures of 200° C. and above.
  • the mixtures according to the present invention can be used in concentrations of from 0.05 to 10.0% by weight, based on the material to be stabilised. Preferred concentrations are from 0.05 to 5.0% by weight, especially from 0.1 to 2.5% by weight.
  • Examples of synthetic lubricating oils include lubricants based on: a diester of a diprotonic acid with a monohydric alcohol, e.g. dioctyl sebacate or dinonyl adipate; a triester of trimethylolpropane with a monoprotonic acid or a mixture of such acids, e.g. trimethylolpropane tripelargonate or tricaprylate or mixtures thereof; a tetraester of pentaerythritol with a monoprotonic acid or a mixture of such acids, e.g.
  • pentaerythritol tetracaprylate or a complex ester of monoprotonic or diprotonic acids with polyhydric alcohols, e.g. a complex ester of trimethylolpropane with caprylic and sebacic acid or of a mixture thereof.
  • Suitable elastomers are familiar to the person skilled in the art. Especially suitable are natural and synthetic rubbers, for example polymers of butadiene and copolymers thereof with styrene or acrylonitrile, and isoprene or chloroprene polymers.
  • polymers to be protected is formed by polycondensates, which can be protected from oxidative and light-induced degradation both in the state of the condensed macromolecular end product and in the state of the low molecular weight starting materials by the addition of the mixtures described hereinbefore.
  • This class includes especially the polyurethanes, which can be stabilised by the addition of dinonyldiphenylamines to, for example, the polyols on which they are based.
  • the mixtures of the present invention can also be added to natural and synthetic organic substances that are pure monomeric compounds or mixtures thereof, for example mineral oils, animal or vegetable oils, waxes and fats, or oils, waxes and fats based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates), and blends of synthetic esters with mineral oils in any desired weight ratios, as are used, for example, as spinning preparations, and aqueous emulsions thereof.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • the mixtures of the present invention can be added to natural and synthetic emulsions of natural or synthetic rubbers, e.g. natural rubber latex or latexes of carboxylated styrene/butadiene copolymers.
  • the stabiliser-containing compositions may additionally comprise other co-additives which are added to improve the properties, e.g. further anti-oxidants, metal passivators, rust inhibitors, viscosity index improvers/melting point or pour point depressors, dispersants/detergents and wear protection additives or extreme pressure/anti-wear additives and friction improvers.
  • co-additives which are added to improve the properties, e.g. further anti-oxidants, metal passivators, rust inhibitors, viscosity index improvers/melting point or pour point depressors, dispersants/detergents and wear protection additives or extreme pressure/anti-wear additives and friction improvers.
  • Alkylated monophenols e.g. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols or nonylphenols branched in the side-chain, e.g.
  • Alkylthiomethylphenols e.g. 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
  • Hydroquinones and alkylated hydroquinones e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl-stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6
  • Tocopherols e.g. ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers e.g. 2,2′-thio-bis(6-tert-butyl-4-methylphenol), 2,2′-thio-bis(4-octylphenol), 4,4′-thio-bis(6-tert-butyl-3-methylphenol), 4,4′-thio-bis(6-tert-butyl-2-methylphenol), 4,4′-thio-bis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
  • 2,2′-thio-bis(6-tert-butyl-4-methylphenol 2,2′-thio-bis(4-octylphenol), 4,4′-thio-bis(6-tert-butyl-3-methylphenol), 4,4′-thio-bis(6-tert-butyl-2-methylphenol), 4,4′-thio-bis(3,6-di-sec-a
  • Alkylidene-bisphenols e.g. 2,2′-methylene-bis(6-tert-butyl-4-methylphenol), 2,2′-methylene-bis(6-tert-butyl-4-ethylphenol), 2,2′-methylene-bis[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 2,2′-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2′-methylene-bis(6-nonyl-4-methylphenol), 2,2′-methylene-bis(4,6-di-tert-butylphenol), 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-ethylidene-bis(6-tert-butyl-4-isobutylphenol), 2,2′-methylene-bis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylene-bis[6-( ⁇ , ⁇ ,
  • O-, N- and S-benzyl compounds e.g. 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzylether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate.
  • Hydroxybenzylated malonates e.g. dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, di[4-(1,1,3,3-tetramethylbutyl)-phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Hydroxybenzyl aromatic compounds e.g. 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds e.g. 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris
  • Benzylphosphonates e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.
  • Acylaminophenols e.g. 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)-isocyanurate, N,N′-bis(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trime
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)-isocyanurate, N,N′-bis(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trio
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)-isocyanurate, N,N′-bis(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane
  • esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)-isocyanurate, N,N′-bis(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • Amides of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
  • p,p′-di-tert- octyldiphenylamine 4-n-butylaminophenol, 4-butyrylamino-phenol, 4-nonanoylamino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylamino-phenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4′-diamino-diphenylmethane, 4,4′-diamino-diphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diamino-diphenylmethane, 1,2-di[(2-methyl-phenyl)-amino]ethane, 1,2-di(phenylamino)propane, (o-tolyl)-biguanide, di[4-(1′,3′-dimethyl
  • metal deactivators e.g. for copper:
  • Benzotriazoles and derivatives thereof e.g. 4- or 5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole, 5,5′-methylenebis-benzotriazole; Mannich bases of benzotriazole or tolutriazole such as 1-[di(2-ethylhexyl)aminomethyl]-tolutriazole and 1-[di(2-ethylhexyl)aminomethyl]-benzotriazole; alkoxyalkybenzotriazoles such as 1-(nonyloxymethyl)-benzotriazole, 1-(1-butoxyethyl)-benzotriazole and 1-(1-cyclohexyloxybutyl)-tolutriazole.
  • 4- or 5-alkylbenzotriazoles e.g. tolutriazole
  • derivatives thereof 4,5,6,7-tetra
  • 1,2,4-Triazoles and derivatives thereof e.g. 3-alkyl (or aryl)-1,2,4-triazoles, Mannich bases of 1,2,4-triazoles such as 1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole; acylated 3-amino-1,2,4-triazole.
  • 3-alkyl (or aryl)-1,2,4-triazoles Mannich bases of 1,2,4-triazoles such as 1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole; acylated 3-amino-1,2,4-triazole.
  • Imidazole derivatives e.g. 4,4′-methylenebis(2-undecyl-5-methyl)imidazole, bis[(N-methyl)-imidazol-2-yl]carbinol-octyl ether.
  • Sulfur-containing heterocyclic compounds e.g. 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and derivatives thereof; 3,5-bis[di(2-ethylhexyl)amino-methyl]-1,3,4-thiadiazolin-2-one.
  • Amino compounds e.g. salicylidene-propylenediamine, salicylaminoguanidine and salts thereof.
  • Organic acids, their esters, metal salts, amine salts and anhydrides e.g. alkyl- and alkenyl-succinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- and alkenyl-succinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxy-carboxylic acids such as dodecyloxyacetic acid, dodecyloxy(ethoxy)-acetic acid and amine salts thereof, and N-oleoyl-sarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic acid anhydrides, e.g. dodecenylsuccinic acid anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol and amine salts thereof.
  • Nitrogen-containing compounds e.g.:
  • I Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates, and 1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
  • organic and inorganic acids e.g. oil-soluble alkylammonium carboxylates, and 1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
  • Heterocyclic compounds e.g.:
  • Phosphorus-containing compounds e.g.:
  • Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates are included in the following paragraphs.
  • Barium dinonylnaphthalenesulfonates calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and salts thereof.
  • Glycerol derivatives e.g:
  • Glycerol monooleate 1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols, 1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols, 2-carboxyalkyl-1,3-dialkylglycerols.
  • Polyacrylates polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinyloyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers, polyethers.
  • Sulfur- and/or phosphorus- and/or halogen-containing compounds such as sulfurized olefins and vegetable oils, zinc dialkyldithiophosphates, alkylated triphenylphosphates, tritolylphosphate, tricresylphosphate, chlorinated paraffins, alkyl and aryl di- and tri-sulfides, amine salts of mono- and di-alkylphosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyltriazole, di(2-ethylhexyl)aminomethyltolyltriazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, 3-[(bis-isopropyloxy-phosphinothioyl)thio]-propionic acid ethyl ester, triphenylthiophosphate (triphenylphosphorothioate), tris(alkylphenyl)phosphorothi
  • the autoclave used is equipped with a reflux condenser having a water separator, electrical heating means, propeller stirrer, temperature-recording means and a device for taking samples.
  • the reactions may be carried out under a nitrogen atmosphere or after previous evacuation of the autoclave.
  • the autoclave is filled with 40 g of diphenylamine and the latter is melted at 80°. 119.5 g of tripropylene (Exxon, U.S.A.) and 4.0 g of the catalyst FULCAT 22B (Laporte) are then added.
  • the autoclave is heated to 205-210° over a period of 45 minutes. At 210°, the pressure of the reaction mixture rises to 3.8 bar absolute pressure. The temperature is maintained at 210° for half an hour and is then reduced over a period of one hour to 156°. Thereafter, the reaction mixture is maintained at 156° for a further six hours.
  • the catalyst is allowed to settle in the reaction vessel over a period of one hour and the reaction mixture is then removed by sucking away the liquid above the catalyst clay deposited.
  • the small amount of clay removed at the same time is separated off completely by filtration through a suction-filter having a pore size of approx. 1-3 ⁇ m.
  • a suction-filter having a pore size of approx. 1-3 ⁇ m.
  • Example 2 Example 1 U.S. Pat. No. 3,496,230 components (% by area) (% by area) diphenylamine 0.3 1.1/1.1 monononyldiphenylamine 25.6 25.4/25.4 dinonyldiphenylamine 71.5 67.4/67.7 trinonyldiphenylamine 2.6 6.1/5.8
  • the reaction is carried out under a nitrogen atmosphere in a heatable 1000 ml glass reaction vessel having a water separator and reflux condenser.
  • the reaction vessel is equipped in addition with a propeller stirrer, a thermometer, a sample-taking device and heat-transfer-medium heating means.
  • the reaction vessel is filled with 150 g of diphenylamine and the latter is melted at 80°. 111.9 g of tripropylene (Exxon, U.S.A.) and 15.0 g of the catalyst FULCAT 22B (Laporte) are then added.
  • the reaction mixture is stirred at 500 rev/min (revolutions per minute) and heated to boiling point to remove the water from the acid catalyst earth.
  • the reaction temperature is increased to 175-180°.
  • 336 g of nonene are metered in over a period of 10 hours.
  • the reaction temperature falls to 155-158°.
  • the reaction mixture is maintained under reflux conditions for a further 5 hours.
  • Working-up is carried out analogously to Example 1.
  • HPDSC High Pressure Differential Scanning Calorimetry
  • the instrument used is a DSC27HP apparatus of the METTLER TA-8000 series (Mettler-Toledo, CH-Gräsee)
  • DSC heat flow to the sample measured as the difference of the heat flows to the sample crucible and the reference crucible. Heat adsorption by the sample indicates an endothermic reaction, e.g. a melting process.
  • a sample crucible containing 45 mg of a defined oil additive mixture is positioned together with an inert reference crucible, both made of steel, on the DSC sensor.
  • the sealed cell is thoroughly flushed several times with the reaction gas, oxygen, and then placed under a pressure of 10 bar. At a heating rate of 50°/min, heating from room temperature to the reaction temperature of 200° is carried out.
  • a sample crucible containing 45 mg of a defined oil additive mixture is positioned together with an inert reference crucible, both made of steel, on the DSC sensor.
  • the sealed cell is thoroughly flushed several times with the reaction gas, oxygen with 400 ppm nitric oxides, and then placed under a pressure of 8 bar. At a heating rate of 50°/min, heating from room temperature to the reaction temperature of 200° is carried out.
  • the induction period is used as the evaluation criterion.
  • the induction period is the period in which the oxidation reaction visibly commences, formed by the point where the base line of the sensor intersects the tangent of the reaction signal.
  • the TA-Station TAS810 used is based on the UNIX operating system, and Mettler Graphware TA3.00 is used as the evaluation software.
  • test are carried out using different reaction procedures.
  • the autoclave is charged in each test with 40 g of diphenylamine. Thereafter, the weight ml of tripropylene and m2 of the catalyst FUL-CAT 22B (Laporte) are added.
  • the autoclave is evacuated to 20 mbar and heated to 140° to remove the water from the catalyst.
  • the autoclave is then sealed and heated to the temperature T1 over a period of 15 minutes. Thereafter, the metering-in of dl grams of tripropylene per hour for a period of time t1 is commenced.
  • the temperature is maintained at the temperature T1 for a period of time t2 and is then reduced over a period of time t3 to the final temperature T2. Thereafter, the reaction mixture is maintained at that temperature T2 with stirring, for a period of time t4. During the reaction, a maximum pressure of p1 bar absolute pressure builds up.
  • the reaction mixture is analysed by means of the gas chromatography method described in Example 1.
  • the product composition without tripropylene data can be seen from Table 1.
  • the percentages relate to percentages by area which can be determined by the gas chromatography method described in Example 1.
  • Example 2 Analogously to the experimental set-up, working-up and analysis of Example 2, tests are carried out using different reaction procedures.
  • the glass reactor of Example 2 is charged in each test with 150 g of diphenylamine. Thereafter, the weight m1 of tripropylene and m2 of the catalyst FULCAT 22B (Laporte) are added and the reaction mixture is heated to reflux temperature under normal pressure to remove the water from the catalyst. Thereafter, the reaction mixture is maintained under reflux for a period of time t2. Thereafter, the metering-in of d1 grams of tripropylene per hour for a period of time t1 is commenced, as a result of which the reaction temperature falls to a temperature T1 owing to the lower boiling temperature.
  • the reaction mixture is finally maintained at reflux, with stirring, for t3 hours, as a result of which a final temperature T2 is reached.
  • the reaction mixture is analysed by means of the gas chromatography method described in Example 1.
  • the product composition without tripropylene data can be seen from Table 2.
  • the percentages relate to percentages by area which can be determined by the gas chromatography method described in Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US09/503,264 1997-06-06 2000-02-14 Nonylated diphenylamines Expired - Lifetime US6315925B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/503,264 US6315925B1 (en) 1997-06-06 2000-02-14 Nonylated diphenylamines

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH137797 1997-06-06
CH1377/97 1997-06-06
US9065198A 1998-06-04 1998-06-04
US09/503,264 US6315925B1 (en) 1997-06-06 2000-02-14 Nonylated diphenylamines

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US9065198A Continuation 1997-06-06 1998-06-04

Publications (1)

Publication Number Publication Date
US6315925B1 true US6315925B1 (en) 2001-11-13

Family

ID=4209007

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/503,264 Expired - Lifetime US6315925B1 (en) 1997-06-06 2000-02-14 Nonylated diphenylamines

Country Status (19)

Country Link
US (1) US6315925B1 (enExample)
JP (3) JP4833387B2 (enExample)
KR (1) KR100624206B1 (enExample)
CN (1) CN1135221C (enExample)
BE (1) BE1013124A3 (enExample)
BR (1) BR9802365A (enExample)
CA (1) CA2240971C (enExample)
CZ (1) CZ294662B6 (enExample)
DE (1) DE19824790B4 (enExample)
ES (1) ES2151819B1 (enExample)
FR (1) FR2764887B1 (enExample)
GB (1) GB2325929B (enExample)
IT (1) ITMI981274A1 (enExample)
NL (1) NL1009331C2 (enExample)
RU (1) RU2198870C2 (enExample)
SG (1) SG65759A1 (enExample)
SK (1) SK285027B6 (enExample)
TW (1) TW555733B (enExample)
ZA (1) ZA984871B (enExample)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040211113A1 (en) * 2003-04-04 2004-10-28 Duyck Karl J. Diphenylamine alkylated with olefin mixtures containing fractions with varying degrees of activity
US20040214813A1 (en) * 2003-04-17 2004-10-28 Crompton Corporation Alkylated iminodibenzyls as antioxidants
WO2005097728A1 (en) * 2004-04-01 2005-10-20 Ciba Specialty Chemicals Holding Inc. Alkylated pana and dpa compositions
US20050230664A1 (en) * 2004-04-14 2005-10-20 Duyck Karl J Ketone diarylamine condensates
US20060094607A1 (en) * 2004-11-04 2006-05-04 Devlin Mark T Lubricating composition
US20060205981A1 (en) * 2003-11-25 2006-09-14 Duslo A.S. Antioxidant compositions of octylated diphenylamines and method of their preparation
US7145038B1 (en) 2005-12-14 2006-12-05 Chemtura Corporation Alkylation of a diphenylamine compound in ionic liquid
US20060276677A1 (en) * 2005-06-02 2006-12-07 Elnagar Hassan Y Process for synthesizing alkylated arylamines
US20070135657A1 (en) * 2005-12-14 2007-06-14 Hobbs Steven J Alkylation of N'-phenyl-N-alkylphenylenediamines in ionic liquid, N'-phenyl-N-alkyl (alkylphenylene) diamines produced thereby, and lubricant compositions containing same
US20070142245A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Dibenzo[b]perhydroheterocyclic amines and lubricating oil compositions
US20070142243A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Synergistic lubricating oil composition containing a mixture of a benzo[b]perhydroheterocyclic arylamine and a diarylamine
US20070142246A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions
EP1939169A2 (en) 2006-12-28 2008-07-02 Chevron Oronite Company LLC Method to prepare nonylated diphenylamine using recycle and sequential temperatures
WO2008154334A1 (en) 2007-06-08 2008-12-18 Infineum International Limited Additives and lubricating oil compositions containing same
US20080318815A1 (en) * 2007-06-20 2008-12-25 Chevron Oronite Company Llc Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a dairylamine
RU2346029C2 (ru) * 2007-03-27 2009-02-10 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" Способ получения антиокислительной присадки к смазочным маслам
US20100130396A1 (en) * 2008-11-24 2010-05-27 Chemtura Corporation Antioxidant compositions
WO2015057487A1 (en) 2013-10-14 2015-04-23 Chemtura Corporation Fixed bed process for clay catalyzed alkylation of aromatic amines
WO2016014380A1 (en) 2014-07-21 2016-01-28 Chemtura Corporation Selective alkylation method for producing p, p'-di-alkylated diphenylamine antioxidants
EP3064273A1 (en) 2015-03-03 2016-09-07 Chemtura Corporation Regeneration of clay catalysts for alkylation of aromatic rings
WO2017011159A1 (en) 2015-07-15 2017-01-19 Chemtura Corporation Diaryl amine antioxidants prepared from branched olefins
WO2018125567A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition with alkylated naphthylamine
WO2018125569A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition including n-alkylated dianiline
EP3114160B1 (en) 2014-03-03 2020-04-15 SI Group Switzerland (CHAA) GmbH Antioxidant compositions
WO2022108298A1 (en) * 2020-11-17 2022-05-27 Songwon Industrial Co., Ltd. Compositions comprising alkylated diphenylamines with improved properties
WO2024158648A1 (en) 2023-01-24 2024-08-02 The Lubrizol Corporation Lubricating composition with phenolic antioxidant and low active sulfur
WO2024206388A1 (en) 2023-03-31 2024-10-03 Lanxess Corporation Efficient, low-energy, low waste alkylation and arylation method for producing safe, enviromentally-friendly disubstituted diphenylamine antioxidants
WO2025024623A1 (en) 2023-07-27 2025-01-30 The Lubrizol Corporation Lubricating composition with phenolic antioxidant, calcium salicylate detergent, and low active sulfur
WO2025088375A1 (en) * 2023-10-27 2025-05-01 Infineum International Limited Lubricant compositions containing high c9 disubstituted diphenylamine antioxidant content
US12486467B2 (en) 2021-06-25 2025-12-02 Songwon Industrial Co., Ltd. O-alkylated sterically hindered antioxidants

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2513669B2 (ja) 1987-03-26 1996-07-03 東レ株式会社 引裂直線性のある二軸延伸ポリエステルフイルム
SG65759A1 (en) * 1997-06-06 1999-06-22 Ciba Sc Holding Ag Nonylated diphenylamines
US6684759B1 (en) 1999-11-19 2004-02-03 Vladimir Gorokhovsky Temperature regulator for a substrate in vapor deposition processes
US6871700B2 (en) 2000-11-17 2005-03-29 G & H Technologies Llc Thermal flux regulator
RU2476587C2 (ru) * 2010-11-12 2013-02-27 Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации Смазочная композиция высокотемпературного масла для теплонапряженных газотурбинных двигателей сверхзвуковой авиации
CN102659606B (zh) * 2012-05-07 2014-04-09 常州大学 一种色泽稳定的烷基化二苯胺抗氧剂的制备方法
CN106699677B (zh) * 2016-12-28 2019-07-09 利安隆（中卫）新材料有限公司 紫外线吸收剂uv-571的制备方法
CN115254088B (zh) * 2022-08-30 2023-11-21 华东理工大学 一种生产烷基二苯胺的催化剂及其制备方法和应用
CN120818190A (zh) * 2025-09-17 2025-10-21 天津利安隆新材料股份有限公司 一种生橡胶组合物以及抗老化剂组合物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2776994A (en) 1954-03-03 1957-01-08 Goodrich Co B F Preparation of a solid diphenylamine antioxidant
US2943112A (en) 1957-11-06 1960-06-28 Pennsalt Chemicals Corp Alkylation of diphenylamine
FR1508785A (fr) 1966-02-17 1968-01-05 American Cyanamid Co Procédé pour la préparation de dialkyldiphénylamines
US4739121A (en) 1984-05-24 1988-04-19 The B. F. Goodrich Company Process for otho- and para-alkylating diphenylamines
US4824601A (en) * 1983-12-08 1989-04-25 Ciba-Geigy-Corporation Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobutylene
EP0387979A1 (en) 1989-01-13 1990-09-19 Nippon Oil Company, Limited Use of a p,p'-Dinonyldiphenylamine in a composition having a reduced tendency to form sludge in oil
US5672752A (en) * 1995-09-13 1997-09-30 The Bfgoodrich Company Liquid alkylated diphenylamine antioxidant
US5750787A (en) * 1995-09-13 1998-05-12 B. F. Goodrich Company Liquid alkylated diphenylamine antioxidant

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1083606A (en) * 1975-04-18 1980-08-12 Vipin M. Kothari Process of preparing para styrenated diphenylamine.
JPS58108296A (ja) * 1981-12-21 1983-06-28 Sumitomo Chem Co Ltd 燃料油用液状酸化防止剤
JPS60202845A (ja) * 1984-03-28 1985-10-14 Seikou Kagaku Kk 白度または透明度の高いｐ−置換ジフエニルアミン類の製造法
JPS6197378A (ja) * 1984-10-18 1986-05-15 Toyoda Gosei Co Ltd エアダクト用シ−ラント
US4769164A (en) * 1987-05-22 1988-09-06 The Lubrizol Corporation Anti-oxidant products
US4798684A (en) * 1987-06-09 1989-01-17 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
RU2015959C1 (ru) * 1992-07-06 1994-07-15 Александр Константинович Аветисов Способ получения дифениламина
JPH0959227A (ja) * 1995-08-11 1997-03-04 Seiko Kagaku Kk スチレン化ジフェニルアミンの製造方法
SG65759A1 (en) * 1997-06-06 1999-06-22 Ciba Sc Holding Ag Nonylated diphenylamines

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2776994A (en) 1954-03-03 1957-01-08 Goodrich Co B F Preparation of a solid diphenylamine antioxidant
US2943112A (en) 1957-11-06 1960-06-28 Pennsalt Chemicals Corp Alkylation of diphenylamine
FR1508785A (fr) 1966-02-17 1968-01-05 American Cyanamid Co Procédé pour la préparation de dialkyldiphénylamines
GB1143250A (en) 1966-02-17 1969-02-19 American Cyanamid Co The preparation of mono- and di-alkyl-diphenylamines
US3496230A (en) 1966-02-17 1970-02-17 American Cyanamid Co Process for mixture of mono- and dialkyl-diphenylamines
US4824601A (en) * 1983-12-08 1989-04-25 Ciba-Geigy-Corporation Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobutylene
US4739121A (en) 1984-05-24 1988-04-19 The B. F. Goodrich Company Process for otho- and para-alkylating diphenylamines
EP0387979A1 (en) 1989-01-13 1990-09-19 Nippon Oil Company, Limited Use of a p,p'-Dinonyldiphenylamine in a composition having a reduced tendency to form sludge in oil
US5186852A (en) 1989-01-13 1993-02-16 Nippon Oil Co., Ltd. P,p'-dinonyldiphenylamine and composition containing the same
US5672752A (en) * 1995-09-13 1997-09-30 The Bfgoodrich Company Liquid alkylated diphenylamine antioxidant
US5750787A (en) * 1995-09-13 1998-05-12 B. F. Goodrich Company Liquid alkylated diphenylamine antioxidant

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Derwent Abstract 1983-726633 [31] for JP 5810826.
Derwent Abstract 1986-165254 [25] for JP 61097378.
Webster's New Universal Unabridged Dictionary, Deluxe Second Edition, Abbreviations Commonly Used in Writing and Printing, pp. 100-101.

Cited By (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7189875B2 (en) 2003-04-04 2007-03-13 Crompton Corporation Diphenylamine alkylated with olefin mixtures containing fractions with varying degrees of activity
WO2004089870A3 (en) * 2003-04-04 2004-11-18 Crompton Corp Process for producing alkylated diphenylamines
RU2369596C2 (ru) * 2003-04-04 2009-10-10 Кемтура Корпорейшн Дифениламин, алкилированный олефиновыми смесями, содержащими фракции с различной степенью активности
US20040211113A1 (en) * 2003-04-04 2004-10-28 Duyck Karl J. Diphenylamine alkylated with olefin mixtures containing fractions with varying degrees of activity
US20040214813A1 (en) * 2003-04-17 2004-10-28 Crompton Corporation Alkylated iminodibenzyls as antioxidants
US6930183B2 (en) 2003-04-17 2005-08-16 Crompton Corporation Alkylated iminodibenzyls as antioxidants
US7928265B2 (en) 2003-11-25 2011-04-19 Duslo A.S. Antioxidant compositions of octylated diphenylamines and method of their preparation
US20060205981A1 (en) * 2003-11-25 2006-09-14 Duslo A.S. Antioxidant compositions of octylated diphenylamines and method of their preparation
WO2005097728A1 (en) * 2004-04-01 2005-10-20 Ciba Specialty Chemicals Holding Inc. Alkylated pana and dpa compositions
US8030259B2 (en) 2004-04-01 2011-10-04 Ciba Speciality Chemicals Corp. Alkylated PANA and DPA compositions
KR101239143B1 (ko) * 2004-04-01 2013-03-11 시바 홀딩 인코포레이티드 알킬화된 ｐａｎａ 및 ｄｐａ 조성물
US20080274925A1 (en) * 2004-04-01 2008-11-06 Beat Michael Aebli Alkylated Pana and Dpa Compositions
US7816308B2 (en) * 2004-04-14 2010-10-19 Crompton Corporation Ketone diarylamine condensates
US20050230664A1 (en) * 2004-04-14 2005-10-20 Duyck Karl J Ketone diarylamine condensates
US20060094607A1 (en) * 2004-11-04 2006-05-04 Devlin Mark T Lubricating composition
US8202829B2 (en) * 2004-11-04 2012-06-19 Afton Chemical Corporation Lubricating composition
US20060276677A1 (en) * 2005-06-02 2006-12-07 Elnagar Hassan Y Process for synthesizing alkylated arylamines
WO2006130498A1 (en) * 2005-06-02 2006-12-07 Albemarle Corporation Improved process for synthesizing alkylated arylamines
US7390928B2 (en) 2005-12-14 2008-06-24 Chemtura Corporation Alkylation of N′-phenyl-N-alkylphenylenediamines in ionic liquid, N′-phenyl-N-alkyl (alkylphenylene) diamines produced thereby, and lubricant compositions containing same
US7563929B2 (en) 2005-12-14 2009-07-21 Chemtura Corporation Alkylation of N′-phenyl-N-alkylphenylenediamines in ionic liquid and N′-phenyl-N-alkyl(alkylphenylene) diamines produced thereby
US7145038B1 (en) 2005-12-14 2006-12-05 Chemtura Corporation Alkylation of a diphenylamine compound in ionic liquid
RU2418784C2 (ru) * 2005-12-14 2011-05-20 Кемтура Корпорейшн Алкилирование производного дифениламина в ионной жидкости
US20070135657A1 (en) * 2005-12-14 2007-06-14 Hobbs Steven J Alkylation of N'-phenyl-N-alkylphenylenediamines in ionic liquid, N'-phenyl-N-alkyl (alkylphenylene) diamines produced thereby, and lubricant compositions containing same
WO2007070264A1 (en) * 2005-12-14 2007-06-21 Chemtura Corporation Alkylation of a diphenylamine compound in ionic liquid
US20070142245A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Dibenzo[b]perhydroheterocyclic amines and lubricating oil compositions
US7501386B2 (en) 2005-12-21 2009-03-10 Chevron Oronite Company, Llc Synergistic lubricating oil composition containing a mixture of a benzo[b]perhydroheterocyclic arylamine and a diarylamine
US20070142246A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions
US20070142243A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Synergistic lubricating oil composition containing a mixture of a benzo[b]perhydroheterocyclic arylamine and a diarylamine
US7285518B2 (en) 2005-12-21 2007-10-23 Chevron Oronite Company Llc Dibenzo[b]perhydroheterocyclic amines and lubricating oil compositions
US8003583B2 (en) 2005-12-21 2011-08-23 Chevron Oronite Company Llc Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions
US8828916B2 (en) * 2006-12-28 2014-09-09 Chevron Oronite Company Llc Method to prepare nonylated diphenylamine using recycle sequential temperatures
EP1939169A2 (en) 2006-12-28 2008-07-02 Chevron Oronite Company LLC Method to prepare nonylated diphenylamine using recycle and sequential temperatures
SG144117A1 (en) * 2006-12-28 2008-07-29 Chevron Oronite Co Method to prepare nonylated diphenylamine using recycle and sequential temperatures
US20080161216A1 (en) * 2006-12-28 2008-07-03 Chevron Oronite Company Llc Method to prepare nonylated diphenylamine using recycle and sequential temperatures
RU2346029C2 (ru) * 2007-03-27 2009-02-10 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" Способ получения антиокислительной присадки к смазочным маслам
WO2008154334A1 (en) 2007-06-08 2008-12-18 Infineum International Limited Additives and lubricating oil compositions containing same
US7683017B2 (en) 2007-06-20 2010-03-23 Chevron Oronite Company Llc Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a diarylamine
US20080318815A1 (en) * 2007-06-20 2008-12-25 Chevron Oronite Company Llc Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a dairylamine
US20100130396A1 (en) * 2008-11-24 2010-05-27 Chemtura Corporation Antioxidant compositions
US8110532B2 (en) * 2008-11-24 2012-02-07 Chemtura Corporation Antioxidant compositions
WO2015057487A1 (en) 2013-10-14 2015-04-23 Chemtura Corporation Fixed bed process for clay catalyzed alkylation of aromatic amines
US9617201B2 (en) 2013-10-14 2017-04-11 Chemtura Corporation Fixed bed process for clay catalyzed alkylation of aromatic amines
EP3114160B1 (en) 2014-03-03 2020-04-15 SI Group Switzerland (CHAA) GmbH Antioxidant compositions
WO2016014380A1 (en) 2014-07-21 2016-01-28 Chemtura Corporation Selective alkylation method for producing p, p'-di-alkylated diphenylamine antioxidants
US9890346B2 (en) 2014-07-21 2018-02-13 Lanxess Solutions Us Inc. Selective alkylation method for producing p, p′-di-alkylated diphenylamine antioxidants
EP3064273A1 (en) 2015-03-03 2016-09-07 Chemtura Corporation Regeneration of clay catalysts for alkylation of aromatic rings
US9744531B2 (en) 2015-03-03 2017-08-29 Lanxess Solutions Us Inc. Regeneration of clay catalysts for alkylation of aromatic rings
US10487043B2 (en) 2015-07-15 2019-11-26 Lanxess Solutions Us Inc. Diaryl amine antioxidants prepared from branched olefins
WO2017011159A1 (en) 2015-07-15 2017-01-19 Chemtura Corporation Diaryl amine antioxidants prepared from branched olefins
WO2018125567A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition with alkylated naphthylamine
WO2018125569A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition including n-alkylated dianiline
US11162048B2 (en) 2016-12-27 2021-11-02 The Lubrizol Corporation Lubricating composition with alkylated naphthylamine
WO2022108298A1 (en) * 2020-11-17 2022-05-27 Songwon Industrial Co., Ltd. Compositions comprising alkylated diphenylamines with improved properties
US12203045B2 (en) 2020-11-17 2025-01-21 Songwon Industrial Co., Ltd. Compositions comprising alkylated diphenylamines with improved properties
US12486467B2 (en) 2021-06-25 2025-12-02 Songwon Industrial Co., Ltd. O-alkylated sterically hindered antioxidants
WO2024158648A1 (en) 2023-01-24 2024-08-02 The Lubrizol Corporation Lubricating composition with phenolic antioxidant and low active sulfur
WO2024206388A1 (en) 2023-03-31 2024-10-03 Lanxess Corporation Efficient, low-energy, low waste alkylation and arylation method for producing safe, enviromentally-friendly disubstituted diphenylamine antioxidants
WO2025024623A1 (en) 2023-07-27 2025-01-30 The Lubrizol Corporation Lubricating composition with phenolic antioxidant, calcium salicylate detergent, and low active sulfur
WO2025088375A1 (en) * 2023-10-27 2025-05-01 Infineum International Limited Lubricant compositions containing high c9 disubstituted diphenylamine antioxidant content
EP4545621A3 (en) * 2023-10-27 2025-06-18 Infineum International Limited Lubricant compositions containing high c9 disubstituted diphenylamine antioxidant content

Also Published As

Publication number Publication date
ZA984871B (en) 1998-12-07
JPH1112234A (ja) 1999-01-19
ITMI981274A1 (it) 1999-12-05
JP2012197462A (ja) 2012-10-18
BR9802365A (pt) 2000-03-28
CN1135221C (zh) 2004-01-21
CN1201781A (zh) 1998-12-16
NL1009331A1 (nl) 1998-12-08
SK74398A3 (en) 1999-04-13
GB2325929A (en) 1998-12-09
SK285027B6 (sk) 2006-04-06
ES2151819A1 (es) 2001-01-01
JP5650692B2 (ja) 2015-01-07
KR19990006677A (ko) 1999-01-25
BE1013124A3 (fr) 2001-10-02
ES2151819B1 (es) 2001-08-16
CZ171698A3 (cs) 1998-12-16
SG65759A1 (en) 1999-06-22
KR100624206B1 (ko) 2006-12-05
RU2198870C2 (ru) 2003-02-20
DE19824790A1 (de) 1999-04-15
FR2764887B1 (fr) 2004-04-02
NL1009331C2 (nl) 2001-05-08
CZ294662B6 (cs) 2005-02-16
DE19824790B4 (de) 2013-06-20
JP4833387B2 (ja) 2011-12-07
CA2240971A1 (en) 1998-12-06
GB9811583D0 (en) 1998-07-29
GB2325929B (en) 2001-08-29
CA2240971C (en) 2008-02-12
TW555733B (en) 2003-10-01
FR2764887A1 (fr) 1998-12-24
JP2009197026A (ja) 2009-09-03

Similar Documents

Publication Publication Date Title
US6315925B1 (en) Nonylated diphenylamines
KR100274361B1 (ko) 디티오인산 유도체, 이를 함유하는 조성물 및 윤활 첨가제로서의 용도
US8030259B2 (en) Alkylated PANA and DPA compositions
US20020065201A1 (en) Lubricants with 5-tert.-butyl-4-hydroxy-3-methylphenyl substituted fatty acid esters
KR100402709B1 (ko) (벤조)트리아졸라디칼과의화합물
EP4247922B1 (en) Compositions comprising alkylated diphenylamines with improved properties
US5507963A (en) Condensation products of melamine, (benzo) triazoles and aldehydes
CA2586083A1 (en) Benzotriazole compositions
MXPA98004486A (es) Difenilaminas noniladas
JPH06199852A (ja) 無リン潤滑剤添加剤
JPH07304772A (ja) メラミン、（ベンゾ）チアゾールおよびアルデヒドの縮合生成物
US4963276A (en) Lubricant composition
MXPA06011062A (es) Composiciones pana y dpa alquiladas

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA SPECIALTY CHEMICALS CORP., NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:AEBLI, BEAT MICHAEL;EVANS, SAMUEL;GATI, SANDOR;REEL/FRAME:012026/0434

Effective date: 19980421

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12